Mold release agent



United States Patent 3,253,032 MOLD RELEAE AGENT Roy A. White, Somers,and Rudolph D. Deanin, West Hartford, Conn, assignors to EthylCorporation, New York, N.Y., a corporation of Virginia No Drawing. FiiedMar. 25, 1963, Ser. No. 267,832 20 Claims. (Cl. lilo-38.22)

This invention relates to new compositions of matter which areparticularly useful as mold release agents or lubricants in moldingprosesses. This invention further re lates to the use of thesecompositions as mold release agents.

In the past many of the techniques of molding particular polymers andplastics has remained an art. Skillful molders developed their ownparticular techniques and tricks to increase the moldability of theirparticular product. One development in this area has been theapplication and study of efficient lubricants as integral parts ofmolding powders or in the application of the lubricants to the moldingsurfaces by themselves. Because of high molding pressures the moldedpart is forced against the mold surfaces under extreme pressures. Inmany instances the particular substances being molded do not contrast inthe mold and a means must be provided for aiding the release of thepiece from the mold surface. Various lubricants have been devised tofacilitate the removalof the molded object. The lubricants generallyhave included mineral waxes, vegetable waxes, fatty acids and metallicsoaps. However, none of these individual lubricants or mold releaseagents have been found effective in all phases of molding. For example,some lubricants are semi-compatible with the particular cured resins andsweat out or bloom if used in large amounts. Other lubricants which areincompatible tend to form a lamination on the surface of the moldedobject, Still other lubricants create a surface on the molded objectwhich prevents printing, stenciling or painting. Lubricant polymers suchas polytetrafiuoroethylene are dilficult to formulate and use becausethe polymeric product is practically resistant to all solvents. Thus ameans for applying polytetrafluoroethylene to the surface of moldingplates has been extremely difiicult to find.

It is therefore an object of the present invention to provide newcompositions of matter which overcome many of the undesirable qualitiesof prior art mold lubricants. It is still a further object to providenew compositions of matter which are valuable as mold release agents andwhich are applicable to a wide variety of molding operations. It isstill a further object of the present invention to provide a process forapplying the new compositons as external lubricants to the particularmolding apparatus, Other objects will be apparent from the descriptionof the invention given below.

The above and other objects are fulfilled by the pro vision of acomposition adapted for use as a mold release agent consistingessentially of a polymer of an alpha olefinic hydrocarbon said polymerhaving a molecular weight of at least 1000 and having in themonomermolecular from about 16 to about 34 carbon atoms and an inert organicdiluent having a boiling point of from' about -80 C. to about 200 C. anda melting point of below about 25 C. The polymer is associated with theinert organic diluent in a concentration of from about 0.01 to aboutweight percent and the diluent is maintained in the liquid state ofaggregation.

It is important that the physical properties of the inert organicdiluent be such that when applied to a hot molding surface of a moldingmachine the diluent is dissipated or rapidly evaporated by heat of saidplate. Thus when a polymer as described hereinabove is suspended orassociated with the diluent and the mixture is applied to the 3,253,932Patented May 31, 1966 hot molding surface of a molding machine, thediluent i is dissipated by the heat leaving a continuous film of polymeron the molding surface of said plate, The type of diluent preferablyemployed would generally depend on the boiling point of the diluent, thetype of polymer being molded, the molding temperature, and the moldingtechnique employed. One could thus conceivably employ a diluent with aboiling point of over 200 C. if the molding temperature was such thatthe diluent would be dissipated. Likewise, one could also employ adiluent with a boiling point of below C. if the diluent is capable ofbeing maintained in the liquid state of aggregation. The diluent shouldhave a melting point of below about 25 C. since it is necessary to mixthe polymer, as described hereinabove, with the diluent. It ispreferable to employ a diluent having a boiling point of from about 30C, up to about C. and a melting point of below about 25 C. which iscapable of being maintained in the liquid state of aggregation since adiluent having properties within these ranges is easy to employ andgives excellent results.

Typical examples of groups of diluents which may be employed arealiphatic, cycloaliphatic, aromatic hydrocarbons or halogenatedderivatives of these. Hydrocarbon mixtures and ethers including alkylethers, cyclic ethers, glycol ethers may be employed. Ketones andcommercial Freon type propellants can also be employed. A few examplesof the preferred solvents are toluene, benzene, 1,1,1-trichloroethane,dichlorodifluoromethane and the like.

The polymer of the alpha olefinic hydrocarbon is further characterizedby generally having a molecular weight of from about 500 up to about50,000. It is preferable that the polymer have a molecular weight offrom about 1000 up to about 45,000. It is most particularly preferredthat the polymer have a molecular weight of from about 200-0 up to about20,000 Within these molecular weight ranges, excellent mold releaseproperties are experienced, coupled with easy application of the polymerto molding surface of the molding apparatus.

These molecular weight ranges may also be expressed in terms of inherentviscosity. The inherent viscosity of the polymer will generally rangefrom about 0.1 up to about 5.0. The preferred inherent viscosity rangesfrom about 0.5 up to about 2.5.

The polymer can either be dissolved in the diluent or can be suspendedtherein It is preferable to dissolve the polymer in diluent sincesolution is easier and good.

results are obtained.

' The concentration of polymer in diluent generally ranges from about0.001 weight percent up to about 25 weight percent based on the diluent.It is preferred that the concentration of polymer in the diluent be fromabout 0.01 weight percent up to about 10 weight percent since excellentmold release results are experienced within this range. It isparticularly preferred that the concentration of polymer be from about0.1 weight percent up to about 5 weight percent. When the preferredconcentrations of polymer are employed, excellent lubrication of themolding surfaces of the molding machine is achieved with,

essentially no clouding and the surface of the molded object is notgreasy or laminated.

The polymeric olefin is further defined as being derived from anolefinic monomer having from about 16 up to about 34 carbon atoms. Thevinyl or alpha olefinic monomer generally has the formula RCH=CH whereinR is an alkyl group having from about 14 up to about 32 carbon atoms.The monomer may either be in an essentially pure state or a mixture ofmonomers. In some instances olefins having beta branches may be presentin which instance the number of carbon atoms in the monomer will remainthe same, i.e., 16-34. It is preferable that the terminal monoolefinichydrocarbon have from about 18 to about 32 carbon atoms since polymersderived therefrom when admixed with a diluent exhibit excellentlubrication properties. It is most particularly preferred that theolefin monomer be either octadecene-1 or a mixture of alpha olefinshaving from 18 to about 32 carbon atoms. These particularly preferredolefins are economical, easily obtained and give excellent results as amold lubricant.

Typical examples of the alpha olefins employed in the present inventionare hexadecence-l, heptadecene-l, octadecene-l, nonadecene-l,eicoscene-l, heneicoscene-l, do-' cocene-l, tricocene-l, tetracocene-l,pentacocence-l, hexacocene-l, heptacocene-l, octacocene-l, nonacocene-l,triacontacene-l, hentriacontacene-l, dotriacontacene-l,tritriacontacene-l, tetratriacontacene-l, 2-ethyl-hexadecene- 1,Z-ethyl-octadecene-l, Lmethyl-octadecene-l, 2-ethyldococene-l,2-butyl-octadecene-1, 2-ethyl-tricontacene-1 and the like.

The term mixtures as used hereinabove may be defined as physicalmixtures of two or more terminal monoolefinic hydrocarbons having fromabout 16 up to about 34 carbon atoms so long as at least two of theolefins differ from each other in carbon content by at least one andpreferably two carbon atoms. Typical examples of these olefin mixturesare: two component systems such as hexadecene- 1 and octadecene-1; threecomponent systems such as octadecene-1, eicoscene-l, and dococene-l;four compo nent systems such as octadecene-1, dococene-l, tetraocene-l,and hexacocene-l. Other systems comprising a mixture of through 18different olefins including beta branched olefins are within the ambitof this invention.

The preferred mixture of olefins having a components thereof is themixture comprising olefins spanning the range of from 18 carbon atoms upto 32 carbon atoms, i.e., octadecene-1, nonadecene-l, eicoscene-l,heneicoscene-1, dococene-l, tricocene-l, tetracocene-l, pentacocene-l,hexacocene-l, heptacocene-l, octacocene-l, nonacocene-l,triacontacene-l, hentriacontacene-l, and dotriacontacene-l. This mixtureof alpha olefins may vary over a wide latitude. For example the olefinswith the even number of carbon atoms are generally much in predominancecomprising from about 90 to about 100 percent of the mixture. However,in many instances equal weight percentages of each of the olefins may bepresent including beta branched olefins.

The most particularly preferred mixture of olefins are those in whicheach have an even number of carbon atoms, the individual alpha olefinichydrocarbons differ in carbon content predominantly in increments oftwo. Thus, the particularly preferred mixture of terminal monoolefinichydrocarbons comprises octadecene-1, eicoscene-l, dococene-l,tetracocene-l, hexacocene-l, ootacocene-l, triacontacene-l, anddotriacontacene l. The percentages of the respective olefins present inthe preferred mixture are subject to wide variation. Generally, theoctadecene is the predominate olefins present and constitutes from about20 percent to about 80 percent of the mixture with the remainder beingthe other olefins in various amounts.

The olefins described hereinabove may be obtained by any general priorart chain growth process. They may also be obtained through modernrefinery techniques. One such chain growth technique is set forth inU.S. Patent 2,699,457 to Ziegler issued January 11, 1955.

The alpha olefins are generally polymerized by the use of a catalystsystem consisting of an alkyl aluminum compound and a salt of arefractory metal. An example of this catalyst is triethyl aluminum andtitanium tetrachloride. Generally, the temperature may vary from about0-150 C. and at a pressure of from about atmospheric up to about 100atmospheres. One general technique which may be employed is set forth byC. 5. Marvel in the Journal of Polymer Science No. 152, pp. 335-353(1961). The Marvel article described polymerizing octadecene-1 employingas the catalyst triisobutyl aluminum and titanium tetachloride in anormal heptane solution. The ratio of triisobutyl aluminum to titaniumranged from about 1:1 down to about 0.8:3. The percent conversion ofpolyoctadecene ranged up to 100 percent.

For best results, when employing the novel compositions of thisinvention as a mold release agent, it is necessary that essentially allof the catalyst be removed from the polymer after the polymerizationprocess. In other words, the polymeric alpha olefin must besubstantially free from any catalyst or catalyst residue. If thecatalyst remains in the polymer, the efiiciency of the polymer anddiluent as a mold release agent is sharply diminished. For example,

the presence of the catalyst in some instances can cause a polymerlamination, i.e., mold release agent laminated on the molded item, orthe catalyst can cause discoloration,' cloudiness, sticking ordegradation of the plastic being molded.

The removal of the catalyst may generally be accomplished by washing thealpha olefinic polymer with an alcohol such as methanol. Prior arttechniques of catalyst removal may also be employed such as two phasesolvent systems found in US. Patent 2,886,561 to W. B. Reynolds et al.issued May 12, 1959.

Another embodiment of the present invention is a composition adapted foruse as a mold release agent consisting essentially of (1) a polymer ofan alpha olefinic hydrocarbon said polymer having a molecular weight ofat least about 1000 and having in the monomer molecule from about 16 toabout 34 carbon atoms; (2) an organic diluent having a boiling point offrom about C. to about 200 C. and a melting point of below about 25 C.;(3) water; and (4) a surfactant. The concentration of polymer isgenerally from about 0.01 weight percent up to about 20 weight percentbased on the total Weight of emulsion. However, concentrations ofpolymer ranging up to about 50 weight percent may be employed in manyinstances. The ratio of solvent to water from about 0.5:1 up to about4:1 and preferably from about 0.821 up to about 2:1. The surfactant isgenerally employed in a concentration of about 0.1% up to about 10%based on the weight of the polymer.

The surfactant may be further defined as a surface active agent which isa compound that reduces the surface tension when dissolved in water orwater solutions. In other words, the surfactant affects the interfacialtension between two liquids. Typical classes of these surfactantsinclude anionic emulsifiers such as soaps and organic sodium sulfonate;nonionic emulsifiers such as polyethers; and cationic emulsifiers suchas quaternary ammonium compounds. Hydrophilic colloids may also beemployed, typical examples of which are carboxymethyl cellulose,hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, proteins,polyvinyl pyrrolidone and the like.

, A further embodiment of the present invention is the process oflubricating the molding surfaces of molding machines or apparatuscomprising the steps of: (1) coating said surfaces with a compositionconsisting essentially of a polymer of an alpha olefinic hydrocarbon,said polymer' being characterized by having a molecular weight ofat-least about 1000 and having in the monomer molecule from about 16 toabout 34 carbon atoms and an inert organic diluent having a boilingpoint of from about 80 C. to about 200 C. and a melting point of belowabout 25 C.,' said polymer being associated with said diluent in aconcentration of about 0.01 to about 10 weight percent; (2) thereaftermolding the plastic in the molding machines; and (3) recovering themolded product.

A still further embodiment of the present invention is the process oflubricating the molding surfaces of molding machines or apparatus whichcomprises the steps of (l) coating said surfaces with a compositionconsisting essentially of a polymer of an alpha olefinic hydrocarbonwherein the polymer is characterized by having a molecular weight of atleast about 1000 and having in the monomer molecule from about 16 toabout 34 carbon atoms; an inert organic diluent; water; and a surfactantand thereafter (2) molding the plastic in the molding machine, and (3)recovering the molded product.

Still another feature of this invention is the process of lubricatingthe molding surfaces of molding machines or apparatus which comprisesthe steps of (1) coating said surfaces with a composition consistingessentially of a polymer of an alpha olefinic hydrocarbon wherein thepolymer is characterized by having a molecular weight of at least about1000 and having in the monomer molecule from about 16 to about 34 carbonatoms, (2) molding the plastic in the molding machines, and (3)recovering the molded product.

The processes of applying the mold release agent to the molding surfacesof a machine is applicable to techniques such as calendering,compression molding, injection molding, jet molding and the like.

The advantages of the compositions and processes of this invention aremany in number. Unlike the prior art external lubricants there is notackiness or caking in the cylinder of an injection molding machine whenthe lubricants of this invention are employed. No cloudiness or bubblingis experienced and no lamination with the molded product is observed.Furthermore, products which have been molded in the presence of theexternal lubricants of this invention possess in general a surface whichis not impaired to painting or printing or evenlabeling with adhesivetape. Over and above the enumerated advantages is the fact that thelubricants of this invention are extremely economical, a definiteadvantage over prior art lubricants such as silicones.

The compositions of this invention and the processes by which they areapplied will be better understood .by the following examples in whichall parts are by weight unless otherwise specified.

EXAMPLE I Preparation of polymer.Essentially pure octadecene-l (20parts) was added to a reactor equipped with a high speed stirrer andcontaining 1.3 parts of n-heptane. 3.5 parts per hundred of triisobutylaluminum and 1.1 parts 'per hundred of titanium tetrachloride were mixedand EXAMPLE II Preparation of polymer.Ten parts of a mixture of alphaolefins having the composition comprising about 50% octadecene-leicoscene-l 6 10% dococene-l 7% tetracocene-l 5% hexacocene-l 3%octacocene-l 3% triacontacene-l 2% dotriacontacene-l was added to areaction vessel equipped with a high speed stirrer and containing 25.4parts of heptane. To this mixture was added 0.18 part by volume oftriethyl aluminum and 0.07 part by volume of titanium tetrachloride. Themixture was maintained at a temperature of 40-45" C. at atmosphericpressure with stirring for 68 hours. After this reaction period thepolymeric product was washed with methanol. The polymer of the olefinicmixture of O -C was obtainedin an 82 percent yield and had an inherentviscosity of 1.2.

Formulation of the polymeric mixture of the olefinicmixture.Eighty-seven (87) parts of toluene was heated in a reactionvessel to about 5 0 C. To this Warm toluene was added 16 parts of thepolymeric olefinic mixture. The solution was stirred until the polymericmixture was dissolved therein.

Other alpha olefins and mixtures of alpha olefins which may bepolymerized and compounded, with equally good results, in accordancewith Examples I and II are nonadecene-l, heneicoscene-l, triacocene-l,pentacocene-l, heptacocene-l, nonacocene-l, hentriacontacene-l and thelike.

Other solvents which may be employed in compounding the resultantpolymer are dichlorodifiuoromethane, tetrafluoromethane,trichlorotrifiuoroethane, monobromotrifluoromethane, diisopropylketone,trichlorobenzene, diethylether, benzene and the like.

EXAMPLE III Application of the formulations of Examples I and II. Chromeplated steel molding plates were scratched with emery paper to resembleold scoured molding plates. These plates were thereafter cleaned withmethyl ethyl ketone. After drying the plates, a 2 percent solution ofpolyoctadecene-l as prepared in Example I was applied to the surface ofthe plates. One half gram of nylon 66 was preheated between the platesin an 8" Preco press for two minutes. The nylon was then molded for oneminute at 550 F. at 40,000 pounds of pressure and thereafter cooled.Another set of molding plates were treated with the solution as preparedin Example II and the molding of nylon 66 was repeated. The results areset forth in Table I. Each of the moldings were rated according to theease of separating the plates, that is the difiiculty of separating theplates which are pressing the resin. The moldings were also rated as tothe ease of removing the molded film from the plates without tearing orripping. The procedure of molding was repeated a second time exceptthat'the plates were not subjected to a second lubricant treatment. Theresults tabulated below for the second molding are rated in the samefashion as in the first molding.

Equally good results are obtained when polyhexadecene, polyheptadecene,polydococene and polydotriacontacene are employed in conjunction withsolvents such as benzene, xylene, methyl cyclohexane, ethylene dichlo- 8The data of Table III demonstrate that each of the mold release agentsof this invention give excellent results both on glass and aluminum.

It should be noted that similar excellent results are ride,trichloromonofluoromethane, octafiuorocyclobutane experienced when eachpolymer of hexacocene, octacoand bromobenzene. cene, triacontacene anddotriacontacene are employed in conjunction with a solvent such asmethyl ethyl ketone, COMPARATIVE EXAMPLE A chloroacetone, heptene,benzene, 1,4-di-t-butyl benzene, trichloroeth lene and erchlorethylene.Nine commercially available mold release agents were y IRA P E B ttested in the same manner as the two lubricants. In 10 COMPAR Y M Laddition to this, a molding was made in which no lubri- Example IV wrepeated with the exception of the Cant Was p y The fatlngs 0f thecommefclally mold release agent employed. Three runs were made onavailable mold release agents W611?v made 1T1 exactly thfi each glassand aluminum employing a commercial silicone same manner as set forth inTable I. Llkewlse, the product, a commercially available polyethyleneglycol product molded in each instance was again nylon 66. and no moldrelease agent. The results obtained are The results of these .nine runsare set forth in Table II. shown in the data listed in Table IV.

Table II First Molding Second Molding Mold Release Agent Not ofDescription This Invention Ease of Ease of Ease of Ease of SeparatingRemoving Separating Removing Plates Molded Film Plates Molded FilmSliIdelPaintable Silicone Mold Silicone Aerosol Fair Fair Fair-Good.

692159. Silicone Spray do Fair-Good Fair-Poor Fair. ReleaseaGen ALecithin Solution Fair Fair-Poor. S-l22 Fluorocarbon Aerosol Vyxdax (alfluorocarbon telomer) Good Good.

QIOSO AcrawaxC Synthetic Ester Amide Fair Fair-Good Very Poor... Poor.Zinc Stearate Powder Poor Fair do Very Poor. Mold-Ease PCR 5.9g; AqueousPolyethylene Good Fair-Poor--- Fair Do.

ye STE-96 Silicone Oil 300 Dinlethy Polysiloxane Silicone Poor Poor lParaifin Wax Very Poor Impossible None do do 1 Turned black, strongfishy odor.

It is thus seen from Example I and Comparative Exam- Table IV ple A thatthe lubricants of the present invention are comparable to manycommercially available agents and Ability to Release in many instancesare superior. It should be further Mold ReleaseAgentNot oiThisInvemionlyesmflmm Mold noted that in the case of paraflin wax that the moldedGlass Aluminum nylon could not be separated from the plate.

The compositions of this invention are further tested in the applicationof molding of polyesters.

EXAMPLE IV A polyester composition was prepared which com.- prisedmixing 100 parts of Naugatuck Vibrin 115-A polyester (an unsaturatedpolyester mixed with a styrene monomer), 0.5 part of a 6 percentsolution of cobalt naphthenate and 1 part of methyl ethyl ketoneperoxide (60 percent solution). The polyoctadecene solution and thecrude polymer solutions of Examples I and II were -each appliedindividually to glass molding plates and Ability to Release Polyesterfrom Mold Mold Release Agent of This Invention .Glass Aluminum PurePolyoctadecene/Toluene Excellent Excellent. Crude 0 -03Po1yalpha-o1efin/Toluene. -do Do.

Silicone Spray 5.9% Aqueous Polyethylene GlyeoL Very Poor Very Poor. Do.

None

Very Poor It is thus seen from Example IV and Comparative Example B,Tables III and IV that the mold release com- EXAMPLE V Two percentsolutions of each polyoctadecene and a mixture of polyolefins having 18to 32 carbon atoms in a toluene solution Was prepared in accordance withExamples I and II. Each of these solutions were applied to a clean glasssurface. A standard epoxy resin formulation was prepared by mixing partsof Shell Epon 828 (which is understood to be a condensation product ofepichlorohydrin and p,p-isopropylidenediphenol), 9 parts of diethylenetriamine and 10 parts of an epoxy modifier (Mod-Epox). The epoxy resinformulation was applied to the treated glass surfaces and the castingswere cured for 18 hours. at room temperature and thereafter at F. for 2hours. Again the respective mold release agents were rated according tothe ease of release from the glass surface. The results of the two testsare demonstrated in Table V below.

9 Table V Mold release agent Ability to release of this invention: epoxyfrom glass Pure polyoctadecene Excellent. Crude C -C poly-alpha-olefinExcellent.

Similar excellent results are experienced when the mixtures of polymericolefins are employed such as hexadecene and octadecene; octadecene,eicoscene and dococene; and octadecene, dococene, tetracocene andhexacocene are employed with solvents such as octafluorocyclobutane,cycloheptane, carbon tetrachloride, and p-cymene.

Comparative runs were made employing a commercially available siliconeoil, a commercially available silicone spray, parafiin and no releaseagent at all. In each of these instances the ease of release or removalof the casting from the mold was again rated and the results tabulatedin Table VI. None of the commercial products tested possessed the moldrelease properties of the compositions of the present invention.

Table VI Mold release agent Ability to release not of this invention:epoxy from glass Silicone oil Very poor. Silicone spray (aerosol) Verypoor. Paraflin wax Very poor. None Very poor.

EXAMPLE VI Thermosetting polyurethanes are also very adhesive duringpolymerization and require mold release agents. A 2 percent solution ofpure polyoctadecene in toluene was made up as in Example I. Scratchedchrome steel molding plates were employed for the castings. To theseclean scratched plates was added the polyoctadecene mold releasesolution. To the treated plates was added thermosetting polyurethane,Nopco Nopcofoam F-202. The polyurethane was cured on the steel platesfor 17 hours at 140 F. The 2 percent solution of polyoctadeceneprovided. good release of foam from the plate.

Three comparative runs were made employing as a mold release agent afluorocarbon and a commercially available silicone spray. No moldrelease agent was applied to the third plate. The results of thesecomparative tests are set out in Table VII below.

Table VII Mold release agent Ability to release not of this invention:foam from plate Fluorocarbon aerosol Very poor. Silicone spray Verypoor. None Very poor.

It is thus noted from the above example that the mold release agent ofthis invention, polyoctadecene, as compared to standard formulationshave excellent mold release characteristics.

EXAMPLE VII Pure polyoctadecene (1 part) produced in Example I was addedto 70 parts of 1,1,1-trichloroethane and 70 parts ofdichlorodifluorornethane. The mixture was stirred at about C. todisperse the polyoctadecene. The mixture was then placed in a containerequipped with a release valve.

EXAMPLE VIII Tests were made employing flame retardant polystyrene asthe resin. In the tests badly scratched, acid etched chrome plated steelmolding plates were coated with 0.13 gram per sq. ft. of the moldrelease agent. The flame retardant polystyrene was applied to the steelplate, which was previously treated with the polyoctadecene of ExampleVII, and molded at 400 F. The

Mold release agent not Ability to release of this invention: from moldFluorocarbon aerosol Fair release (cloudy surface). Silicone spray Poorrelease. None Very poor release.

Table VIII demonstrates the commercially available release agents testedabove were definitely inferior to the product of this invention. Cloudysurfaces have always been a problem in polystyrene molding as well aslubrication. The styrene molded product obtained in Example VIII whenthe polyoctadecene release agent was employed was subjected to paintingwith an aerosol paint without further surface treatment. It was foundthat the polyoctadecene mold release agent did not impair the surface ofthe molded polystyrene product as far as the adherence of the paint wasconcerned.

EXAMPLE IX A polyoctadecene-toluene solution is made up in the samemanner as set forth in Example I. To this solution is added 25% byweight of water. The resultant mix ture is agitated and 0.5 part ofdioctyl sodium sulfosuc' cinate is added. Agitation is continued for afew minutes after the addition of the sodium salt.

The polyoctadecene mixture is applied to the molding surface of badlyscoured chrome plated steel molding plates which are preheated. Thesolution evaporated leaving a coating of polyoctadecene on the surfaceof the plates. One-half gram of nylon 66 is placed on the plates andpreheated for two minutes. The nylon is then molded for one minute at550 F. at 40,000 pounds per square inch and thereafter cooled. The easeof separating the plates is rated as good.

Equally good results are experienced when other poly meric alpha olefinsand mixtures of alpha olefins are compounded with an inert organicdiluent and a surfactant and hydrophilic colloids such as diethyl sodiumsulfosuc cinate, sodium laurate, sodium myristate, potassium myristate,sodium palmitate, carboxymethyl cellulose, methyl cellulose and the likeare employed.

EXAMPLE X The mixture of polymeric alpha olefins of Example I] isapplied in the essentially pure state in the absence of a solvent to thehot surface of chrome plate steel molding plates. This is achieved' bymerely sprinkling the polymer powder on the plates. Nylon 66 is moldedin the same manner as set forth in Example IX. The ability to releasethe molded nylon was rated as good.

It should also be noted that the products of this invention may be usedin molding applications for plastics and resins other than those shownabove with equally good results. Typical examples of other plastics whenthese mold release agents may be employed are polyvinylchloride,phenolic resins, urea-formaldehyde resins, melamine formaldehyde resins,cellulose esters, polycarbonates, acetals and p-olyolefins and the like.

Diluents which may be employed in conjunction with the polyoctadecenemold release agent of this invention are organic diluents having aboiling point of between about C. up to about 200 C. These organicdilvents are generally inert to the polymeric materials which have beendissolved therein. It is preferable that the organic diluents employedbe hydrocarbon diluents having up to about 16 carbon atoms. Thehydrocarbon diluents may be aliphatic, cycloaliphatic, aromatic orhalogenated derivatives of these. It is most preferable to employ eitheraromatic or halogenated hydrocarbons since excellent results areexperienced when these diluents are used. Typical examples of thediluents which may be employed in this invention are benzene, toluene,oxylene, m-xylene, p-xylene, hemi-mellitene, psuedocumene, mesitylene,isodurene, ethyl benzene, 1,2-diiethyl benzene, n-propyl benzene,cumene, n-butyl benzene, tbutyl benzene, p-cymene, allyl benzene,hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane,methyl cyclohexane, methyl cycloheptane, methyl chloride, carbontetrachloride, ethyl chloride, methyene chloride, ethylene dichloride,chloroform, dichloroethylene, tetrachloroethane, pentachloroethane,hexachloroethane, trichlorethylene, perchlorethylene, propylenedichloride, 1,1,1 trichloroethane, l-chloropentane, 'l-chlorobutane,bromobenzene, chlorobenzene, dibromobenzene, trichlorobenzene,p-chlorotoluene, o-chlorotoluene, hexene, heptene, octene, decene, alphadichloroheptene, alpha dibromooctene and the like. Hydrocarbon mixturesmay also be employed typical of which are the turpines, naphthas,gasoline, kerosene and the like. alkylethers, cyclic ethers, glycolethers and the like may be employed. Typical examples of these ethersare ethyl ether, isopropyl ether, n-butyl ether, diamyl ether, n-hexylether, ethylene glycol monomethyl ether, ethylene glycol mono-n-butylether, diethylene glycol monomethyl ether, diethylene glycol mon-oethylether, diethylene glycol monobutyl ether, ethylene glycol diethyl ether,ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, 1,4-

dioxane, 1,2-propy1ene oxide, dimethoxymethane, 2- methyl furan,tetrahydrofuran, dihydropyran, tetrahydropyran, 2,2'-dichloroethyl etherand the like. Ketones may also be employed in this invention typical ofwhich aremethyl isobutyl ketone, methyl ethyl ketone, methyl-npropylketone, hexanone-2, hexanone-3, methyl-t-butyl ketone, di-n-propylketone, diisopropyl ketone, diisobutyl ketone, di-n-amyl ketone,chloroacetone, dichloroacetone, mesityl oxide, cyclohexanone, acetylacetone and the like.

In many instances, it is extremely desirable to employ a commercialpropellant as a diluent. Typical examples of these propellants aretrichloromonofluoromethane, dichlorodifluoromethane,imonochlorotrifluoromethane, monobromotrifiuoromethane,tetrafluoromethane, monochlorodifluoromethane,dichlorotetrafluoromethane, octafluorocyclobutane,tetrachlorodifluoroethane, trichloromonofiuoromethane,trichlorotrifluoroethane and the like.

It should also be noted that the polymers may be compounded with apropellant and another diluent. Typical examples of these combinationsare: trichloromonofluoromethane and 1,1,1-trichloroethane,dichlorodifluoromethane and toluene; monochlorotrifluoromethane andhexane; monobromotrifluoromethane and cyclopentane; tetrafiuoromethaneand the diethyl ether of diethylene glycol and the like.

Typical examples of surfactants Which may be employed in this inventioncan be found in Organic Chemistry, 3rd edition by Fieser and Fieser,Reinhold Publishing Company, pp. 410-415; Surface Active Agents bySchwartz and Perry, 1949, Interscience Publishers, Inc., New York; andSurface Active Agents by Anson et al., Annal of the New York Academy ofScience, volume XLVI, Art 6, pp. 347-530, 1946. Typical of these surfaceactive agents are the polyethylene oxide ether of lauryl alcohol, polyethylene oxide ether of l,1,3,3-tetramethyl butyl phenol, dimethyllauryl-benzyl ammonium chloride, the methosulphate of oleyl amide ofdiethyl ethylene diamine, cetyl pyridinium chloride, sodium sulphonateof heptadecyl vbenzimidazole, sodium sulphate of polyethylene oxideether of 1,1,3,3-tetramethylb utylphenoi, sodium sulphon- 1 Ethers suchas diate of polyethylene oxide ether of 1,1,3,3-tetramethylbutylphenol,sodium sulphate of 2-methy1-7-ethyl-undecanol-4, sodium sulphate of3,9-diethyltridecanol-6, di- (2-ethylbutyl)sodium sulphosuccinate,sodium salt of octyl oleate, sodium salt of octyl isethionate, sodiumsalt of oleyl amide of N-methyl glycine, sodium salt of the lauric esterof sulpho-acetic acid, the condensation product of oleic acid anddegraded protein, octyl benzene sodium sulphonate, diisopropylnaphthalene sodium sulphonate, sodium stearate, cetyl sodium sulphonate,sodium sulphate of lauryl alcohol, sodium sulphate of oleyl alcohol,carboxyrnethyl cellulose, methyl cellulose, hydroxyethyl cellulose,polyvinyl alcohol, polyvinyl pyrrolidone and the like.

The mold release agents of this invention lend themselves to a widevariety of general processing methods or molding techniques. One typicalmethod in which these novel compositions are particularly useful iscompression molding which is a non-continuous method for producingcomplex shapes by the influence of pressure upon a plastic compoundconfined in-a heated mold. Injection molding and jet molding are alsoprocesses in which these novel compositions may be employed. Injectionmolding involves heating a plastic molding powder or granules in anenclosed cylinder to the proper temperature to which pointa pistonpushes the softened plastic through a nozzle along runners into a coolmold. These compositions may be employed both in the enclosed cylinder,the piston or ram and the cold mold. These novel compositions are alsouseful in extruders which is a process of forcing a heat softenedplastic material through an orifice or dye to produce rods or tubes,etc. Other valuable processes such as film casting where the plastic isflowing out on moving belts or wheels are important uses. Calendering isanother process in which these polyolefins may be employed as moldrelease agents or lubricants.

The polymers of this invention may also be employed as internallubricants. Internal lubrication is, of course, achieved by mixing thelubricant material with the polymer to be processed. Accordingly, insome instances moderate amounts of the polymer lubricants employed inthis invention can be used to increase melt fluidity of high molecularweight polymers to be processed. The requirement of a lubricant is thatthe lubricant must be compatible With the high molecular polymers. Aprerequisite for increasing the melt fluidity is that the additive isnot seriously harmed by room temperature properties or heat distortiontemperature. In other instances where the lubricant is incompatible withthe high molecular polymers to be processed, trace amounts of thelubricant can be employed to increase lubricity in the processingtechnique employed such as calendering or molding.

The amount of poly C -C polymer employed will generally depend on theparticular use. If the lubricant is compatible with the high molecularweight polymer amounts ranging from about 1 weight percent up to about40 weight percent may be employed. However, if the lubricant is notcompatible with the high molecular weight polymer then amounts rangingfrom about 0.01 up to about 5 weight percent will be employed.

Polyoctadecene produced as in Example I was milled with polypropylene totest the increase of the melt fluidity of the polymer at hightemperatures. The plasticized polymer was also tested forlow temperatureproperties and strength. The results are given in Example XI and TableIX.

EXAM PLE'XI Polypropylene parts) was milled With- 30 parts of table."The data shows that the melt index of the lubricated polypropylene wasmarkedly increased. This polymer also had excellent low temperatureproperties.

14 agent consisting essentially of polyoctadecene and toluone, saidpolyoctadecene being associated with said tolu- TABLE IX COMPARISON OFPOLYPROPYLENE WITH PLASTICIZED PROPYLENE Melt Index Test Tensile 1 50% 3Polyocta- Yield Ultimate 2 Brittle Shatter 4 dccene Strength,Elongation, Temperaat 13 F.

Tempera- Pressure, Grn./l p.s.i. Percent ture, F. ture, F. p.s.i. Min.

Propylene 0 447 43. 25 4. 63 4, 200 700 85 Yes. I Plasticized Proyplene30 447 43. 25 50 3, 100 300 65 N0.

1 AS'IM D-638, Instron, 0.5lMinutes Pull, 73 F., 50% RH. 1 Measure ofStress.

3 AS'IM D74657T, A6" Thick Bars. 4 30-Mil sheet struck sharply by handagainst edge of freezer.

Similar excellent results are obtained when a polymeric mixture ofolefins containing from 16 to 32 carbon atoms are employed (thecomposition of Example II); eicoscene- 1, dococene-l, tetracocene-l,hexacocene-l and the like.

The polymers employed in this invention find additional uses as alubricant for plastics such as nylon rollers, window tracks, slidingdoors and the like.

Having thus described embodiments of the present invention it is notdesired to be bound except as set forth in the following claims.

Having thus described embodiments of the present invention it is notdesired to be bound except as set forth in the following claims:

We claim:

1. A composition adapted for use as a mold release agent consistingessentially of a polymer of an alpha olefinic hydrocarbon said polymerhaving a molecular weight in the range of from about 1000 up to about45,000 and having in the monomer molecule from about 16 to about 34carbon atoms and an inert organic diluent having a boiling point of fromabout 80 C. to about 200 C. and a melting point of below about 25 C.,said polymer being associated with said diluent in a concentration ofabout 0.01 to about weight percent, the balance of said compositionbeing diluent, said diluent being maintained in the liquid state ofaggregation.

2. The composition of claim 1 wherein said diluent is furthercharacterized in that it is a halogenated hydrocarbon solvent.

3. The composition of claim 1 wherein said diluent is1,1,1-trichloroethane.

4. The composition of claim 1 wherein said diluent is furthercharacterized in that it is an aromatic hydrocarbon solvent.

5. The composition of claim 1 wherein said diluent is toluene.

6. The composition of claim 1 wherein said olefinic hydrocarbon has fromabout 18 up to about 32 carbon atoms in the monomer molecule.

7. The composition of claim 1 wherein said olefinic hydrocarbon hasabout 18 carbon atoms in the monomer molecule.

8. The composition of claim 1 wherein said olefinic hydrocarbon is amixture of olefins each having between about 18 up to about 32 carbonatoms in the monomer molecule.

9. A composition adapted for use as a mold release agent consistingessentially of polyoctadecene and 1,1,1- trichloroethane saidpolyoctadecene being associated with said 1,1,1-trichloroethane in aconcentration of about 0.01 weight percent up to about 10 weight percentbased on the 1,1,1-trichloroethane.

10. A compositionadapted for use as a mold release Temperature at which50% of the bar are brittle.

molding machines comprising coating said surfaces with the compositionof claim 1.

13. A process of lubricating the molding surfaces of molding machinescomprising coating said surfaces with the composition of claim 9.

14. A process of lubricating the molding surfaces of molding machinescomprising coating said surfaces with the composition of claim 10.

15. A process of lubricating the molding surfaces of molding machinescomprising coating said surfaces with the composition of claim 11.

16. A composition adapted for use as a mold release agent consistingessentially of (l) a polymer of an alpha olefinic hydrocarbon, saidpolymer having a molecular weight of at least about 1000 and having inthe monomer molecule from about 16 to about 34 carbon atoms, (2) anorganic diluent having a boiling point of from about C. to about 200 C.and a melting point of below about 25 C.; (3) water; and (4) asurfactant.

17. The composition of claim 16 wherein said olefinic hydrocarbon hasfrom about 18 to about 32 carbon atoms in the monomer molecule.

18. The composition of claim 16 wherein said polymer is polyoctadecene.

19. The process of lubricating the molding surfaces of molding machinescomprising coating said surfaces with the composition of claim 16. v

20. The process of lubricating the molding surfaces of molding machinescomprising coating said surfaces with the composition of claim 18.

References Cited by the Examiner UNITED STATES PATENTS 2,500,165 3/1950Doherty et a1. 260683.l 2,500,162 3/1950 Seger et al 260683.1 2,543,0162/1951 Grosse 260677 2,580,654 1/1952 Browning 25215 3,118,838 1/1964Scherer 252-15 ALEXANDER H. BRODMERKEL, Primary Examiner.

MORRIS LIEBMAN, Examiner.

J. B. EVANS, Assistant Examiner.

1. A COMPOSITION ADAPTED FOR USE AS A MOLD RELEASE AGENT CONSISTING OF APOLYMER OF AN ALPHA OLEFINIC HYDROCARBON SAID POLYMER HAVING A MOLECULARWEIGHT IN THE RANGE OF FROM ABOUT 1000 UP TO ABOUT 45,000 AND HAVING INTHE MONOMER MOLECULE FROM ABOUT 16 TO ABOUT 34 CARBON ATOMS AND AN INERTORGANIC DILUENT HAVING A BOILING POINT OF FROM ABOUT -80*C. TO ABOUT200*C. AND A MELTING POINT OF BELOW ABOUT 25*C., SAID POLYMER BEINGASSOCIATED WITH SAID DILUENT IN A CONCENTRATION OF ABOUT 0.01 TO ABOUT10 WEIGHT PERCENT, THE BALANCE OF SAID COMPOSITION BEING DILUENT, SAIDDILUENT BEING MAINTAINED IN THE LIQUID STATE OF AGGREGATION.